Cationic ring-opening polymerization of hexamethylcyclodisilazane: General aspects and tentative mechanisms

The ring-opening polymerization of hexamethylcyclodisilazane (D_2NMe), initiated by methyl triflate in 1,2-dichloroethane, forms in the first, fast kinetic step both linear polymer and cyclic dimer (D_4NMe). Subsequently a slow depolymerization process occurs leading to exclusively cyclotrisilazane (D_3NMe). On the basis of kinetic measurements carried out using an adiabatic calorimetric technique and complementary experiments, mechanisms of both propagation, cyclization and back-biting reactions are proposed. The influence of the reaction temperature was also studied; it is demonstrated that, at low temperature, polymerization does not lead to cyclic oligomer formation. In such conditions, the polymerization presents a ‘living’ character.     

Photovoltaic collectors efficiency according to their integration in buildings

A model for building integrated photovoltaic systems has been developed and implemented in a dynamic simulation tool. This tool takes into account the thermal interactions between the PV collector and the building. The influence of the type of integration upon the PV collector efficiency has been evaluated and hybrid PV/air collectors have been studied. An overall efficiency is defined, including the production of electricity and heat. A case study has been performed on two different typical buildings. In the case of a multi-crystalline silicon PV collector integrated on the roof of a single family house located in Paris, the efficiency of unventilated PV modules fixed on the roof is 14%. If the PV collector is used to preheat the ventilation air, the efficiency reaches 20%. A proper building integration also improves the environmental balance of PV technologies over their life cycle.     

On transitive orientations with restricted covering graphs

We consider the problem of finding a transitive orientation of a comparability graph, such that the edge set of its covering graph contains a given subset of edges. We propose a solution which employs the classical technique of modular tree decomposition. The method leads to a polynomial time algorithm to construct such an orientation or report that it does not exist.     

Microwave heating of poly(ethylene terephthalate) bottle preforms used in the thermoforming process

Thermoforming (free blowing) of poly(ethylene terephthalate) preforms was successfully and quickly performed in a rotating system designed for dielectric hysteresis heating. Temperature profile modeling was carried out with the amorphous poly(ethylene terephthalate) permittivity at different temperatures. The Maxwell and heat equations were used to determine the best profile and power tuning. The determination of the theoretical boundary conditions was accomplished by the adjustment of the numerical transient external surface wall temperature with experimental infrared pyrometry results. In comparison with infrared, microwaves allowed high power density absorption inside the perform wall without a dramatic temperature gradient. Consequently, the heat blowing stage could be accelerated, and the process took at least 5 times less energy than infrared heating. Industrial applications involve the integration of the molding step and the design of the overall process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.     

Aspects of orientation-dependent grain growth in extra-low carbon and interstitial-free steels during continuous annealing

The present work concentrates on the application of orientation imaging microscopy (OIM) based on the electron backscattered diffraction (EBSD) technique to the investigation of the microstructural evolution of an extra-low carbon (ELC) steel and a Ti-Nb-bearing interstitial-free (IF) steel, during continuous annealing. Aspects like the nucleation, the evolution of the recrystallized volume fraction and grain size of grains with different orientations, the interface area limiting recrystallized {111} regions, and the apparent growth rates have been considered. Different criteria have been applied in order to identify crystallites produced during annealing. During the first stages of annealing, a network of grain boundaries with misorientations higher than 10 deg is produced, mainly inside the deformed γ-fiber grains. The crystallites formed within this network, free from cells or subgrains at their interiors, can be considered as potential nuclei. However, among all, only some of them become effective due to an important selection. The {111} recrystallized grains have a significant size and number advantage as compared with other texture components, and a hard impingement between clusters of {111} grains is produced during grain growth. The effect of grain growth behind the recrystallization front seems to be negligible as compared with the grain coarsening produced by the migration of this front, driven by the cold-work stored energy.     

Catalysis, the turntable for a clean future

Upgrading the bottom of the barrel for clean fuel production, developing new engines with optimized catalytic posttreatments, implementing clean catalytic combustion technologies, improving the overall CO₂ balance via catalytic processes and, lastly, developing new water purification techniques represent major upheavals in catalysis linked to refining and environmental protection. This paper, thus, will focus on the determining contribution of catalysis to the most recent achievements in these domains. A technico-economic approach will follow, underlining their main incentives and drawbacks within the framework of future environmental constraints.     

Optimization techniques for curved path computing

Participating media with an inhomogeneous index of refraction make light follow curved paths. Simulating this in a global illumination environment has usually been neglected due to the complexity of the calculations involved, sacrificing accurate physical simulations for efficient visual results. This paper aims to simulate non-linear media in a more reasonable time than previous works without losing physical correctness. Accuracy is achieved by solving the Eikonal equation of geometrical optics, which describes the path followed by a light beam that traverses a non-linear medium. This equation is used in the context of a photon mapping extension.     

Absorbing surface impedances of lossy layers in the finite difference time-domain method

In this paper the time-domain surface impedances of an homogeneous absorber layer, are given for the vertical and horizontal polarizations, or respectively for the electric field perpendicular or parallel to the incidence plane. It turns out that the application of the concept in finite difference time-domain (FDTD) in absorbing surface impedances boundary conditions, gives results in good agreement with analytical Fresnel reflection coefficients.     

Analysis of the effect of polypyrrole synthesis conditions on its capacity to reduce hexavalent chromium

This paper reports the capacity of polypyrrole to reduce toxic hexavalent chromium (Cr(VI)). The influence of using different electrolytes during the polymer's synthesis has been studied. To improve the reduction of Cr(VI), the parameters considered were the polypyrrole morphology and the amount of conducting polymer. Polypyrrole obtained by cyclic voltammetry at a low sweep rate using KBr as supporting electrolyte showed better performance for Cr(VI) reduction compared to coatings obtained by constant potential or cyclic voltammetry at high sweep rates.